Compositions and methods for influencing the growth of plants



United States Patent'O COMPOSITIONS AND METHODS FOR INFLUENC- ING THEGROWTH PLANTS Hans Gysin, Base], and Enrico Knusli, Riehen, near Basel,

Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swissfirm No Drawing. Application December 14,

SerialNo. 398,186

Claims priority, application Switzerland September 2, 1953 I 18 Claims.c1. '71- 23 wherein R represents hydrogen or a low molecular alkylradical, R represents an alkyl group and Ar represents a phenyl radicalsubstituted or unsubstituted as desired,

have attained great importance because of their selective action as weedkillers. Reference is made in this respect to N-phe'nylisopropylcarbamate (IPC) and N- (3-chlorophenyl) -isopropyl carbamate (CIPC)Surprisingly, it has now been found thatlo-phenyl carbamates of thegeneral formula:

Am-CO-O-Ar wherein Ar represents a phenyl or naphthyl radicalunsubstituted or substituted if desired by alkyl, alkoxyoralkylmercapto, amino or substituted amino. or nitro groups or byhalogen, and Am represents a member selected from the group consisting 17 alkyl alkyl cyeloalkyl and A polymethylene N- have very markedinfluence on the growthof-plants.

Depending. on the concentration and formulation as 'well as the mode ofapplication, by which latter is understood'in particular the choice ofthe time of application-and the part of the plant to be treated, theinfluence on the growth of the plant cannotonly ,bean inhibitory butalso a stimulating one. There aretherefore, increased possibilities inpractical application.

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Inhibition or delaying of germination and prolongation of the harveststate of vegetables and fruits, in addition; modification of the leafstructure to increase productivity; delaying the blossom; blossomthinning; desiccation of crop plants; defoliation (complete or partial);selective weed killing; total eradication of plants.

In addition, in certain circumstances, parthenogenesis and production ofseedless fruits can be attained.

Though several of the reactions listed above can often be attained withthe same substance under chosen conditions and in particular, the purelytoxic effects leading to the death of the plant can be caused byincreasing the concentration, there are naturally differences andpreferred indications for the various application purposes which canresult even if the action is, in principle, the same, e. g. from thediflferences in the transportation of the absorbed active substance inthe plant.

Dependent on the intended use and the form of application, theconcentration of the active ingredient in formulations ready for use canvary within wide limits. High concentrations can be'used in particularin'dusts for the treatment of the soil and fairly high concentrationsfrom about 0.1-2% can be used for application to a part of the plantonly, e. g. for powdering the ends of cuttings the root formation ofwhich is to be stimulated. Low concentrations can be used for example inemulsions in which cuttings are dipped or placed for a longer time tostimulate root formation. Very low concentrations can be used also whenthe active ingredients are applied to the soil in water (by watering) orin manure. In soil treatment, there is, in general, no necessaryrelationship between the concentration and the amountof activeingredient taken up by the plant, since a lower concentration of activeingredient can be equalised by increasing the total amount of the agentapplied. There is therefore, a very great range of possibleconcentrations.

Directly dependenton the concentration however, is the amount of activeingredient taken up by the plant when it is applied in aqueoussuspensions and emulsions which are sprayed on to the parts of the plantabove the ground, in particular on to the leaves, up to the runoffpoint. The concentration for such agents lies between about 0.01% and2%. These agents are prepared immediately before use from concentrates,the concentration of active ingredient of which is many times that ofthe agent tobe applied and in cases of concentrates for the preparationof emulsions of liquid active ingredient and for the preparation ofsuspensions of solid active ingredient, the concentration can be as highas about The following compounds for example can be used as activeingredients according to this invention:

dimethyl carbamate B. ewes-100 (4) O (4 n butyl phenyl)- dimethylcarbamate 'B. P.12 -96" (5) O (4 tert. butyl phenyl)- dimethyl carbamateBP o.2 121-123,

(6) 0 4 tert. butyl L 2 methyl phenyl) dimethyl carbamate B. P.0.13108-112",

O (2.6 dimethoxy pheny1)-'dimethy1carbamate B. P. 0.45 135-138",

M. P. 102-103? 0 (2 nitrophenyl) dimethyl carbamate M. P. 5658 'O (4methyl 3 nitrophenyl) dimethyl carbamate M. P. 74-75 0 (3 dimethylaminophenyl) dimethyl carbamate B. P.o.2 134 0 on naphthyl dimethyl carbamateB. P.o.o5 118-120,

M. P. 49-50" 0 p naphthyl dimethyl carbamate M. P. 92-94" 0 (1chloronaphthyl 2)- dimethyl carbamate B. P.o.oa l35-137 M. P. 59-60" 0(2 chloronaphthyl 1)- dimethyl carbamate M. P. 102-104 O (5chloronaphthyl 1)- dimethyl carbamate M. P. 112 0 (4 chloronaphthyl 1)-dimethyl carbamate B. P.o.1a 138-140 0 phenyl N methyl nbutyl carbamateB.-P.u.z 112-113 O (2 methyl phenyl)- N methyl n butyl carbamate B.P.o.2 118-120 O (4 methyl -phenyl)- N-methyl-n-butyl carbarnate B. P.o.2118-121 O-(4-tert. amyl-pheny1)-N- v methyl-n-butyl carbamate..- B.P.o.2 155-1565 0 (2 chlorophenyl) N- dimethyl carbamate B. P.o.15117-119,

O (2 chloro phenyl)- dimethyl carbamate B. P.1z 154-156 0 (4chlorophenyl) di- 1 methyl carbamate B.'P.o.2 1l8-120 O (4 bromophenyl)dimethyl carbamate B. P.o.1a 105 methyl-n-butyl carbamate B. P.o.2135-137 0 (2.4 dichlorophenyl)- N-methyl-n-butyl carbamv 1 1 ate B.P.o.4 144-146.5 O (3 butoxyphenyl)- 1 N-methyl-n-butyl carbam- I 1 ateB. P.p.z148-150 O-phenyl-diethyl carbamate B. P.12 138-142 O (2 methylpheny1)- I I diethylcarbamate B. P.12 144-147 01 (4 methyl -'phenyl)-diethyl carbamate B. P.1z 153 0 (4 tert. amyl-phenyly diethyl carbamateB.'P.o.1s 144,

O (2 chlorophenyl) di- 1 1 ethyl carbamate B. PJrz 155-157 O (2.4dichlorophenyD- diethyl carbamate B. P.d.z 134-135 0 (4 methoxy pheny1)-diethyl carbamate B. P.o.4 129-130 O (4 nitrophenyl) di- 1 p ethylcarbamate B. P.0d: 122 0 (4 amino phenyl)-diethyl carbamate P. 64-65 0(4 acetamido phen-. Y

yl) diethyl carbamate M. P. 94

(41) 0 (3 dimethylaminophenyl)-diethyl carbamt -o-os 139-141 (42) O anaphthyl diethyl carbamate 172-174 (43) O 13 naphthyl diethyl carbamate-o.oo1 125127 (44) O phenyl di n butyl carbamate -P-o.0s100-101 (45) O(2 methyl phenyl)- di-n-butyl carbamate 1 145 (46)'O (4 methyl phenyl)-di-n-butyl carbamate B. P. 0.14126-127" (47) O- (4-tert.amyl-phenyD-din-butyl carbamate B. P.o,07 146-148 (48) O (2chlorophenyl) din-butyl carbamate B. P.0.1 124-125 (49) O (4chlorophenyl) din-butyl carbamate B. P.o.z 146-148 (50) O (2.4dich10rophenyl)- di-n-butyl carbamate B. P.o.2 163-166 (51) O phenyl Nmethyl cyclohexyl carbamate B. P.o.17 127,

' M.P. 66 (52) O (2 methyl phenyl)- N-methyl-cyclohexyl carbamate B.P.12 ISO-153 (53) O (4 methyl phenyl)- N-methyl-cyclohexyl carbamateP.o.15 133-135",

M. P. 64-66.5 (54) O-(4-tert. amy1-phenyl)-N- methyl cyclohexylcarbamate B. P.0.15 177-179 (55) O (2 chlorophenyl) N- methyl cyclohexylcarbamate B. P.0.4 158 (56) O (4 chlorophenyl) N- methyl cyclohexylcarbamate B. P.u.5 161-163 (57) O (2.4 dichlorophenyl)- N methylcyclohexylcarbamate B. P.u.2 163-165 (58) O phenyl pentamethylenecarbamate M. P. 76-78 (59) O a (2 methyl phenyl)- pentamethylcnecarbamate B. P.o.1 145-146". (60) 0 (4 methyl phenyl)- pentamethylenecarbamate M. P. 86-87 (61) O-(4-tert. amyl-phenyl)-pentamethylenecarbamate B. P.u.2 167-168" (62) O (2 -chlorophenyl) pentamethylenecarbamate B. P.o.s 145 (63) O (4 chlorophenyl) pentamthylene carbamateB. P.o.1a 139 (64) O 2.4 dichlorophenylpentamethylene carbamate B.P.o.oe 124 Some of the carbamates are known. The others can be producedaccording to methods known per se. Technically suitable in particular isthe condensation of reactive carbonic acid derivatives such as e. g.carbamic acid halides or isocyanates with phenols or the reaction ofphenolchlorocarbonic esters with amines. Thus for example, p-tert. amylphenyl dimethyl carbamate can be produced as follows:

186 parts of anhydrous sodium salt of p-tcrt. amyl parts of dimethylcarbamyl chloride are added dropwise and the whole is boiled for 12hours under reflux. After cooling, the whole is washed with water and 2N-caustic soda lye and then distilled. 198 parts of the desiredcarbamate are obtained. The carbamate boils at l17-190 at a pressure of0.15 mm. and becomes solid on cooling.

The same compound is obtained by reacting ptert. amyl phenylchlorocarbonic acid ester ('B.'P.1 3;134'135) with two equivalents ofdimethylamine; analogous carbamates result from the reaction ofallyamine, diethylamine, dibutylamine, methyl butylamine, methylcyclohexylamine and piperidine.

As will be described in the following, p-tert. amyl phenyl dimethylcarbamate is distinguished for its rootforming properties.

As starting materials for the production of'other carbamates whichaccording to the invention can be used for influencing plant growth, thefollowing phenols and amines for example are suitable: phenol, 2-cresol,3 -cresol, 4-cresol, dimethyl phenols, isopropyl'p'henols, 4-n-butylphenyl, 4-tert. butyl phenol, 4-tert. amyl phenol, 3.5-ditert. butylphenol, iso-octyl phenols, nonyl phenol, 4- lauryl phenol, 4-cyclohexylphenol, guaiacol, 2-ethoxy phenol, S-methoxy phenol, 4-et hoxy phenol,3-butoxy phenol, 4-methylmercapto phenol, 4-isoamylm'ercapto phenol,2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2.4-dichlorophenol,2.5-dichlorophenol, 3.4-dichlorophenol, pentachlorophenol,4-bromophenol, 2.4.6-tribromophenol, 5-chloro-2-hydroxy toluene,2-chloro-4-amyl phenol, 4-nitrophenol, 4-aminophenol, 3-dimethylaminophenol, 4-acetylaminophenol, l-naphthol, Z-naphthol, 5-chloronaphthol-l, 4-chloronapthol-l, 2-chloronaphthol-l,l-chloronaphthol-Z, 1-hydroxy-tetrhydro-(5.6.7.8)-naphthalene,4-ureidophenol, 4-thioureidophenol, dimethylamine, diethylamine,dipropylamine, di-isopropylamine, dibutylamine, methyl-cyclohexylamine,piperidine.

The active substances can be used in solvents, as emulsions or asdusting agents; the compounding of the active substances dependsentirely on the intended use.

Should a stimulating action be required, then naturally auxiliarysubstances which are as biologically indifferent as possible or are evenbeneficial, will be chosen; on the other hand if a toxic action is thechief consideration, this can be increased by the choice of carriersubstances which themselves have a phytotoxic action.

Solvents such as, in particular, alcohols; ketones such as acetonediacetone alcohol or cyclohexanone; aliphatic hydrocarbons such askerosene, and cyclic hydrocarbons such as benzene, toluene, xylene,tetrahydronaphthalene, alkylated naphthalenes, also chlorinatedhydrocarbons such as tetrachlorethane, ethylene chloride and finallyalso high boiling organic solvents such as mineral and vegetable oils,or mixtures of the above named substances can be used for the productionof solutions.

Chiefly emulsions and dispersions are meant by aqueous forms ofapplication. The substances as such or in one of the above namedsolvents, are homogeneously incorporated into water, preferably by meansof wetting or dispersing agents. On the other hand, concentratessuitable for dilution with water can be produced which consist of activeingredient, emulgator or disperser and possibly, a solvent.

Quaternary ammonium compounds; soap, soft soap, aliphatic sulphuric acidmonoesters having long chains, aliphatic aromatic sulphonic acids,alkoxy acetic acids having long chains; polyethylene ethers of fattyalcoholsand polyethylene condensation products can be named as examplesof cation active, anion active and non-ionogenic emulgating ordispersing agents respectively.

' Dusting agents can be made simply by mixing or grinding together theactive ingredient and a solid carrier. As such solid carriers can benamed: talcum, diatomaceous earth, kaolin, bentonite, calcium carbonate,boric acid, tricalcium phosphate, also powdered wood, powdered cork,charcoal and other materials of vegetable origin. On the other hand thesubstances can also be drawn on to the carriers by means of a volatilesolvent. Pulverulent preparations and pastes can be suspended in waterby the addition of wetting agents and protective colloids. and so usedas spraying agents.

The various forms of application can be adapted to the intended use inthe usual way by the addition of substances which improve thedistribution, the adhesive properties, resistance to rain and, possibly,the penetrating powers. Such substances are, for example, fatty acids,resins, wetting agents, glue, casein or alginates. In the same way, thebiological activity can be increased by the addition of substances whichhave a bactericidal or fungicidal action or of substances which alsoinfluence the growth of plants. Manures may also be added.

. A few chosen examples follow which illustrate the range of applicationdescribed above. The results obtained are also given.

Example 1 15 cuttings from Ligustrum ovalifolium were kept for 48 hoursin anemulsion containing 200 p. p. in. active ingredient. They were thenplanted in sand and kept for 3 After 5 weeks, 8 cuttings had a total of28 roots of an average length of 3.06 cm.; 2 had sprouted no roots. 0fthe 10 controls, 3 cuttings had 6 roots of an average length of 1.63cm., 7 had sprouted no roots.

Thecuttings were then planted again. After another 11 weeks all thetreated cuttings showed 'good top growth and an excellent growth ofroots. Of the controls, 60%

' had died, and the remaining 40% had good growing pointsand fair growthof roots.

Example 2 CH; O C ON/ CHa l0 cuttings from Chamaecyparis pisiferaplumosa were treated with a mixture of 2% of active ingredient and 98%carrier. After 5 weeks all the cuttings had together 60 roots of anaverage length of 1.65 cm. Of the controls, 4 cuttings had 31 roots ofan average length of 1.48 cm., 4 had no roots and 2 had died.

Example 3 C235 mo-b- OOON a CAHQ Soya beans dipped in 15 com. of anemulsion containing 0.5% of active ingredient sprouted roots just overthe place dipped.

The following compounds were found to have a similar stimulating actionon the root formation of various test plants: O-(2-chlorophenyl)-dibutylcarbamate and O-(4- methyl-phenyl)-N-methyl-N-cyclohexyl carbamate.

Example 4,

Soya bean plants 2 weeks old sprayed with an emulsion containing 1% ofactive ingredient lost all their leaves in 3 days.

in 7 days.

.Exampl eS cam.

oooN

-(2.4-dichlorophenyl)-pentamethylene carbamate, for example, has asimilar action.

Example 6 'CHr-CH;

] CHz-Cg ,25-50 seedson filter paper in petri dishes were treated with.cc'm. of anemulsion containing 0.1% of active .ingredient. Observationof the percentage of germinating seeds and of the top growth and rootgrowths showed the .iollowing results (l0=normal growth, 0=no growth):

Radish 7.06 Cucumber 4.99 Rye grass 0 The following compounds forexample have a similar selective inhibitory action on the germinationand growth wherein Ar represents an aryl radical substituted by a memberselected from the group consisting of halogen, alkyl, alkoxy,alkylmercapto, amino, substituted amino and nitro groups, and Amrepresents a member selected fromthe group consisting of alkyl alkylcyclonlkyl N.- alkyl "and 4. Amethodof inducing and stimulating the rootfor- "mation of plant cuttings which comprises treating the .plantcuttings with a compound as defined in claim '1 in an amount andconcentration sufficient to stimulate the which comprises treating theplants with a compound as a definedin claim 1 in an amount andconcentration cient to stimulate the root growth of plants.

root formation of plant cuttings.

5. A method of inducing and stimulating the root formation of plantcuttings, which comprises treating the plant cuttings with O-(4-tert.amyl-phenyl)-dimethyl carbamate in an amount and concentrationsuflicient to in- .duce and stimulate the root formation of plantcuttings.

6. A method of stimulating the growth of the above ground part of plantswhich comprises treating the plants 3 with a compound as defined inclaim 1 in an amount and concentration suflicient to stimulate thegrowth of the above ground part of plants.

7. A method of inhibiting the growth of plants which comprises treatingthe plants with a compound as defined .in claim 1 inan amount andconcentration suflicient to 'in an amount and concentration sufficientto desiccate crop plants.

9. A method of defoliating crop plants which comprises treating theplants with a compound as defined in claim 1 'in an amount andconcentration suflicient to defoliate crop plants.

10. A method of inhibiting weed growth without influencing the growth ofthe crop plant which comprises treating the plant crop with a compoundas defined in claim 1 in an amount and concentration suflicient toinhibit weed growth without influencing the growth of the crop plant.

11. A method of killing plants of all kinds where no vegetation iswanted which comprises treating the plants with acompound as defined inclaim 1 in an amount and concentration sufficient to kill plants of allkinds.

12. A composition for inducing and stimulating the formation of roots ofplant cuttings, comprising O-(4-tert. amyl-phenyl)-dimethyl carbamate inan amount and concentration suflicient to induce and stimulate theformation of rootsof plant cuttings, and a solid powder.

13. A plant growth influencing composition comprising a compound of theformula AmCO-O-Ar wherein Ar represents an aryl radical substituted by amember selected from the group consisting of halogen, alkyl, alkoxy,alkylmercapto, amino, substituted amino and nitro groups, and Amrepresents a member selected from the group consisting of alkyl alkylcycloalkyl alkyl and A polymethylene N-- in an amount and concentrationsuflicient to influence the growth of plants, with-a solid powder ascarrier.

14. A plant growth influencing composition comprising a compound of theformula wherein Ar represents an aryl radical substituted by a member:selected from, the group consisting of halogen,

alkyl, alkoxy, alkylmercapto, amino, substituted iamino and nitrogroups, and Am represents a member selected from the group consisting ofalkyl alkyl cycloalkyl alkyl and polymethylene N- in an amount andconcentration sufficient to influence the growth of plants, with asurface active agent as carrier. 15. A plant growth influencingcomposition comprising a compound of the formula AmCO-O-Ar wherein Arrepresents an aryl radical substituted by a member selected from thegroup consisting of halogen, alkyl, alkoxy, alkylmercapto, amino,substituted amino and nitro groups, and Am represents a member selectedfrom the group consisting of alkyl alkyl cycloalkyl alkyl polymethyleneN- in an amount and concentration suflicient to influence the growth ofplants, with a high boiling organic solvent as carrier.

16. A plant growth inhibiting composition comprising a compound of theformula AmCO-OAr wherein Ar represents an aryl radical substituted by amember selected from the group consisting of halogen, alkyl, alkoxy,alkylmercapto, amino, substituted amino and nitro groups, and Amrepresents a member selected from the group consisting of alkyl alkyloycl alkyl\h and A 1 th 1 N- po yme y ene in an amount and concentrationsuflicient to inhibit the growth of plants, with a solid powder ascarrier.

17. A plant growth inhibiting composition comprising a compound of theformula 10 AmCO-OAr wherein Ar represents an aryl radical substituted bya member selected from the group consisting of halogen, alkyl, alkoxy,alkylmercapto, amino, substituted amino and nitro groups, and Amrepresents a member selected from the group consisting of alkyl N alkyleycloalkyl N. alkyl and wherein Ar represents an aryl radicalsubstituted by a member selected from the group consisting of halogen,

alkyl, alkoxy, alkylmercapto, amino, substituted amino and nitro groups,and Am represents a member selected from the group consisting of alkyl\Nalkyl/ cyeloalkyl N- alkyl and polymethylene N- in an amount andconcentration suflicient to inhibit the growth of plants, with a highboiling organic solvent as carrier.

References Cited in the file of this patent UNITED STATES PATENTSAeschlimann July 16, 1940 Aeschlimann et al Jan. 3, 1950 OTHERREFERENCES Thompson et al.: New Growth-Regulating Compounds, a Summaryof Growth Inhibitory Activities of Some Organic Compounds as Determinedby Three Tests, Botanical Gazette, vol. 107 (1946), pages 475 to 507.

Freed: Correlation of Certain Physical Constants of Some Alkyl Esters ofn-Phenyl Carbamic Acid With Their Phytotoxicity, Science, vol. III (Mar.17, 1950), pages 285 and 286.

I. Am. Chem. Soc., vol. 69, No. 3, Mar. 1947, pages 718 to 722.

Templeman et al.: Nature, vol. 156, Nov. 24, 1945, page 630.

1. A METHOD OF INFLUENCING THE GROWTH OF PLANTS WHICH COMPRISES TREATINGTHE PLANTS WITH A COMPOUND OF THE FORMULA: